Separation of organic compounds



Aprll 14, 1953 H. G. MCGRATH ETAL SEPARATION OF ORGANIC COMPOUNDS Filed March 17, 1949 ATTORNEYS om: 0.52.6 I o .com

Patented Apr. 14, 1953 ziesaii-rl slira-RAflIoNJoacammeoQMroIINnsr Henry-'Gi lVIoGratli;l Elzabetlr;l Herle'rtiJ Passinc Y Engleivocdfand'liouis.C. Rfubiiig-vWest Caldwell;-

N.' JE, assignorsitmTheMiW.' Kelloggfompany, Jltrsey-:Gity,',N.i;J.lascorp'cratiomofrelaware Y ApplicatimrMrclu-L 1949,.seriamm 81,958

17'Clainlsi. Cl. 26m-5mi inventionrelates totira-separation offfOrrV game-'compounds andrelates# morev partioularly`7v to21 tl'eA separationf of'foxygenated organic^-com Qoundsirom-therea'ctionfproduct-obtainedfinthe-- catalytic 'liydrogen'ation ofE oxides; of carbon:l Stili'f more particularly;I the? inventionrelates-rv to-V ajn improved" processi for the separation off' Oxy`h g'enafted crganic-compoundsmresentinta-Water# 1J'rl: 5:luot liquid: pliase-produced-from the'- treatarnentoffthe" reactioni product; obtained'J ir'rV thei catalytic hydrcgenatfion of oxidesof carbon.- Il'his applicationisaflcontinuationhinpartfoffourprior and co-pendingf applicationL Serial* Nov 70928721 ,l'd November :14; 1946, nOW- Patenti-N0: tj'illil", and relating totheseparationofa4 orvl ganiccompounds:

Ii'r'sj` known' that hydrogen and@oxides.of-'fcari` bon; particularlylcarhon;monoxide? may-b`e -made'i Ltoreact-exotliermicalli#inthe-#presenc'eofcertainik aforementioned organic compounds? 4various) methods--are employed; among-them# lo'eii'iirftli'os'ey knownas'xed-bed: andfluidl-bedlcatalystopere 's itions;` Gharacteristically; certain reaction con# ditionsa're necessaryd foreach of1 these processes and'f'Cr tlfie-k particular-1catalyseusedi The syn-- thesis 'feed-leas" or reaction; mixture comprises? a mixtureaof aboutir: 'frnols#A of hydrogem permol' of;V carhorr,monoxide;` and; may be; prepared; by various meanstincluding the;catalyticzoonversion ofnaturalgasgsteamand carboni4 dioxide,- z It'zwill.

understood,- however; .that-l whila the: hydro@ g'cnationof carbon-monoxide@ hasabeen referred: to specifically, suoli-1 above-referred#liydrogenai` tion; vis,-: ,0i`f wider application and! 'includeswitiiin itsv scope the hydrogenati'crr` ofiany: suitable cariiornoxidei4 Y f Thereaction emuent thusy produced in--tlie aforementioned hydrogenatiomof' an oxide;V of carbon, --compris ghydrocarbons; alcohcls,- acids andi other oxygenated-j` organic ccmpound'swhich may]y include aldehydes`; ketones 'and`Y- esters:` is:

obtained in the' vapor vstater'r the form;L offreactorr 2. outlet" gases. 'l'lfiesey gases are" generally* passedv` through one*or-morecondensation zonesirrwhichY theycare cooledfto temperaturesWithinlthe-range'? ofiabout--40F and'about Y150" F.' Theresultingi condensate then separates into` an oil' product# liquid* phaseja water-product' liquid; phase and5 andi mayfal'so' contain minor-proportions of hy-V drocarbonsl andl other;relativ'elyJ low'boilingfoxy genatied organic compounds such" as aldehydes; ketoneshoresters; f

Ir'lour: alcove-'referredi 4priorJ anda" co-pendingapplication Serial No: '709;8'72; We disclosed'` ani'mproved process-forthe treatment ofl the-aforementionedfoil'?produet 1iquidphase fcr-the-separation off ci;ygerratedi4 organic compounds there-- from. They process of# the presentV invention:v is thereforeconcerned-witha seriesl of; novelinterrelatedlsteps which the aforementionedlwater product liquid phaseiseither separatelyl subjec'rtdV totreatmentfrthe separationofJr ox--yev gen'ated' organ-ic` compoundsd` therefrom; or' is treated in-L combinationM with p products obtained fromltlieprioritreatmentofthe oil product---1iquid phase` for the separation of# oxygenated' organicv compoundsv` from the aforesaid Water product liquidphases ItE is; tliereforefan object of'fthe present invention"toprovideanfimproved process-for the separation off o'x'ygenat'edorganic compounds present inA thel Waterf product/ liqudlphase obtained'from the treatment of the reaction efiiuentf producedlin the hydrogenation -ofv oxides'ofz carbone Anotherobject of t-heinvention isto` provide anfir'nprovedlpro'oess for theseparationrofforganic acids, alcohols and'f otherX oxygenatedf organic con'irmund's-v presentiv in@ the Water productivliquid phase` obtained from the treatmenti off the'A` re'- actionkeilluent produced; in`--the'hydrogenationlof oxides-'fo'fscarbons Y Gther objects fand; advantages" inherent in the invention` Will-4 be? ,apparentVd from the: following moredetailed disclosure:

The accompanyingy drawingA illustrates diagrammatically one-- form" ofV the, apparatus employed vand-1capalzile-of;'carryingr out'oneembodii'- mentcfi'theprocessfcff'the invention- While the l inventionwillv be describedin @Retail by reference- 3 to the embodiment illustrated in the drawing, it will be noted that it is not intended that it be limited thereto, but is capable of other embodiments which may extend beyond the scope of the apparatus illustrated. Furthermore, the distribution and circulation of liquids and vapors is illustratedin the drawing by diagrammatic representations of the apparatus employed. Valves, pumps, compressors and other mechanical elements necessary to effect the transfer of liquids and vapors and to maintain,k the conditions of temperature and pressure necessary to carry out" the function of the apparatus, are f omitted in order to simplify the description. It will be understood, however, that much equipment of this nature is necessary and will be supplied by those skilled in the art.

Referring to the drawing, the product of the reaction of a mixture of hydrogen andan oxide of carbon, such as carbon monoxide at varying prising organic acids which are the highest boiling components present in the mixture introduced into tower I1 through line I6, are withdrawn through line I9 as a product of the process and may be subjected to further treatment, such as conventional fractionation for the recovery of individual acid components, which is outside the scope of the present process.

An intermediate boiling fraction from tower I1 comprising an acetaldehyde-free distillate v and/or propionaldehyde-free distillate, is transmethanol and higher alcohols, C2 and higher acids and may also contain aldehydes, ketones and esters depending upon the conditions ofthe reaction. This product is rst cooled to condense substantially large quantities k.of normally liquid components. Conveniently, condensation may be obtained in a plurality of cooling stages which are represented diagrammatically in the drawing by condenser I I with which line Il) connects. From condenser II the resulting mixture of Ycondensate and uncondensed gases passes through line I2 to a separator I3. In the latter, uncondensed gases are withdrawn through line I4 and the condensate separates as a lower aqueous phase and an upper oil phase. Both phases thus obtained containalcoholsracids and other oxygenated organic compounds; those oxygenated compounds of relatively lower molecular weight tend to remain in the water product liquid phase while those of relatively higher molecular weight tend to remain in the oil productliquid phase. The oil product liquid phase thus obtained is drawn off at an intermediate point from separator I3 through line I5, while the water product liquid phase is drawn off from the bottom of separator I3 through line I6. It should be noted that apparatus embodying more than one separation stage may be employed, if desired; for example primary and secondary separation stages may be introduced operating successively and respectively at temperatures of about 150 F. and about 100 F. v

i The aforementioned water product liquid phase withdrawn through line I6 comprises relatively low boiling organic acids, alcohols and may contain hydrocarbons in minor proportion and also other oxygenated organic compounds such as aldehydes, ketones and esters. This product is next transferred through line I6 to a distillation tower I1. In towerA I1 the mixture introduced through line I6 is heated to distill overhead the lowest boiling components of the mixture, namely, the lowest boiling aldehyde components such as acetaldehyde and propionaldehyde, and which are withdrawn through line I8 for further use or treatment outside the scope of the present process. The bottoms obtained from tower. I1 comferred as a side-stream through line 20. This distillate contains relatively low boiling alcohols having from kthree to six carbon atoms per molecule, and may contain aldehydes higher boiling than acetaldehyde or propionaldehyde and mayalso contain traces of organic acids and other oxygenated organic compounds such as ketones and esters. This distillate is next treated with alkali in order to effect neutralization of traces of organic acids that may be present, and also to polymerize aldehydes and to saponify esters. For this purpose, the distillate is next transferred from tower I1 through line 20 -to a caustic treater 2 I, in which it is intimately mixed with alkali in a suitable amount introduced through line 22. After the components of the mixture are maintained in intimate contact for a time sufficient to effect the desired neutralization of traces of organic acids present in the distillate from tower I1, withdrawn through line 20, and to effect polymerization of aldehydes and saponification of esters, the resulting mixture is withdrawn from treater 2| through line 23. The mixture thus withdrawn through line 23 comprises alcohols, alkali salts of organic acids and aldehyde polymers. This mixture is next transferred through line 23 to a separator 24. In separator 24 separationiseffected between an upper phase comprising aldehyde polymers which is withdrawnthrough line 25, and a lower phase comprising a mixtureV of alcohols, alkali salts of organic acids and other oxygenated organic compounds in minor proportion which is withdrawn through line 26. The aldehyde polymers thus withdrawn through line 25 may be transferred for further use or treatment outside the scope of the present process. The aforementioned aqueous mixture inline 26 comprising alcohols, alkali salts of organic acids and other oxygenated organic compounds in minor proportion is next transferred to a distillation tower 21. in tower 21 the mixture is heated to distill overhead alcohols present, which are withdrawn through line 28. The bottoms from tower 21, comprising an aqueous mixture of alkali salts of organic acids, are withdrawn through line 29 and may be subjected to conventional treatment with an inorganic acid in order to regenerate the corresponding organic acids from these salts. Accordingly, the aqueous mixture of alkali salts and organic acids in line 29 is transferred through this line to an acid *regeneration stage as indicated in the drawing. The acids thus regenerated from the aforementioned alkali salts are withdrawn from the acid regeneration stage through line 30 and may be combined with acids withdrawn from tower I1 through line I9 in order to obtain a concentration ofv total acids present in the aforementioned water product liquid phase in line I6. l The overhead from tower 21 comprising a mix ture of alcohols (and also other oxygenated compounds, in minor proportion, such as keltones) may also containminor quantitiesofihy'- 3l at a low point through linei32. Y agent-and the-.aforementioned alcohol mixture A containing hydrocarbons 1 are contacted? in tower 31 @under conditions velective `tofabsorbfn the .agarrar-r1 Vc'iro'carbons which must-'be removed -in order-to leiect recovery of relativelypurealcohols. It has vbeen lfound that the I hydrocarbons tend .taconcentrate as `their homogenous alcohol Iaaeotropes in ythe distillation' cuts taken betweenl the various falcohols. IIn this respect, itlhas beenfound'that in such aqueous alcohol-solutions contaminating .hydrocarbons canbe removed'efliciently by means of a i' relatively low y boiling `hydrocarbon Vwhich isV however, that the 'operation .is not restricted to fthesoleuse of pentane for the purpose indicatedgbutthat `other lighter or heavier hydro- -carbons'may alsofbe successfully employed, such 'as butaneor `heptane,.provided'the boiling point of .the :hydrocarbon treating agent selected is 1ower than thatof the hydrocarbons to be exztracted. i

In order `to effect removal of the aforemenvtioned contaminating hydrocarbons, the over- -head=`from tower21, comprisingvan alcohol mix- 'lture .containing minor quantities of hydrocarbons, is Ltr-ansferredithrough line 28 to an upper Apoint in an extraction tower 3l'. In tower 3| ythe mixture introducedthrough line 28 is subjected to intimate countercurrent contact with pentane :or :other selected suitable hydrocarbon .treatin-g- :agent Vwhich 4is :introduced 'into tower Theltreating treating agent, .the hydrocarbons present. 1 The yextract thus produced, comprising thefpentane 'The vraffinate :treatment y.in Vthe vprocess. lhereinafter described.

VThe extractfrom tower3l comprisingthe pen-- tane treating.: agent and :higher hydrocarbons .to-

v.gather vwith small quantities of alcohols. is ktransie-.lredthrough line 33'to .a .distillation'tower 3 5. A``I rrtotver..35 the aforementioned'mixture is heated to distill overhead th-e pentane treatingagent :andcsmall .quantities .of Aalcohols present as peniztane-alcohol azeotropes vawhich rare :withdrawn 'through line.:3.6. .Bottoms'from'ftower coml-prising 'higher hydrocarbons fare 'withdrawn `througlfil line .3.1 for. further usev or vtreatmentfoutrside'thezscopeof thepresent process.

.Theroverheads from'tower 35 comprising penvtane-alcohol a'zeotropesl .lare ltransferredv through line 36 .into .agmixer- 38,'.whi'ch is vprovided'to` in- Atimately mix/a relatively: small4 amountl offlwater y.with the .alcohol-.pantano VAmixture. 'Water thus v.employed .is :introduced .into imixer: 38 j-through :aline y39.. ".Theresulting :mixture afrommixer- 38 "is Vvessel; -4'1- l.intimately vcontacted withvvater or Withanzaquef nextitransferred'through line 40 to a :separator 4l In1separator4l, by means .of settling action. an :upperp'hase comprising pentaneis .withdrawn through line 32 and is recycled through this line for further use in tower 3l inthe processrhereinbefore described. Make-up pentane is intr `duced into linei32 through linen.

Bottoms from separator 4l, comprising -an aqueous-alcoholmixture containing :small quantities of'pentane, arewithdravvn throughline .43 and combined with the raflinate from tower 32 yin line 3.4 VV.vvhichcontains :a mixture lof alcohols and .relatively minor rquantities of ypentanc as .previously described. The mixture .thus corn'- bineld in line 34 Vis next transferred .intoa diS- :tillationtower-M to `elfect removal lof the pentaneitreating agentfrom thealcohol stream. In tower 44themixture is. heatedto vdistill overhead :,pentane-:alcohol azeotropes (such as pentane- .methanolazeotropem through line 45 and a pen- :tane-.freealcohol mixture withdrawn as bottoms 'through line :4.5, asia-.productor theprocess. .This

mixture of alcohols maybe transferred to conventional fractionation apparatus if so desired. vfor the separation of individual alcohol components. I

The overhead distillate from tower 44, comprising pentane-alcohol azeotropes isl transferred through line 45 into line 36 to .combine with the overhead distillate from `tower 35 .which also comprises pentane-lightalcohol azeotropes. The combined stream is next transferred through line 3 6 into :mixer 38 where it is water-washedfor `rSubsequent processing inthe manner previously described, in order to effect subsequentrecovery of the lightestalcohol component present,.for example, methanol.

.As l previously indicated, the aforementioned Waterproduct liquid-phase, inanother modicavtion oftheprocess of theinvention may betreat- Yed in combination with products obtained from -the'prior' treatmentof. the oil product liquid phase. In accordance with this modificationof the proeessy ofthe invention uncondensed gases iromseparator I3, .withdrawn through line I4 may .be transferred to a low point in a suitable'scrubbing In` this gas scrubber the .gases are y.side the scope of the present process.

The aforementioned oil product ,liquid phase, separatedin separator i3 and withdrawn .through Aline l5, is next transferred vthrough'thisline .to wa. low lpoint .in anoil scrubber 5.0, .in :whichfthe l:oil is vcontacted intimately with water toJabsorb in-the water the oxygenated compounds which are. dissolved'in the oil and are'relatively .more

soluble in'water, such as relatively low :boiling alcohols, Vketones land ialdehydes. The water employed for this .purpose conveniently mayv be the water employed :for scrubbing in gas scrubber :41, whichis transferred from scrubber '4l'. to the upper part of Voil scrubber 5U through'line 5|.. The Ascrubbing water, containing dissolved oxygenated vorganic compounds, is withdrawn 'from the bottom of 'oilscrubber 50 through line52, which Aconvzveniently nonnects with line LE for combining the .relatively narrow boiling fractions.

-the present process.

scrubbing water with the water product liquid phase withdrawn from separator I3. The com- 4bined stream is next transferred through line I6 to tower i1 for further treatment in the process hereinbefore described.

The scrubbed oil in scrubber 50 is withdrawn from an upper portion of the scrubber through line 53." This oil may next be treated with alkali to convert organic acids contained in the oil to their corresponding alkali salts, and also to polymerize aldehydes and saponify esters. For this purpose the oil is transferred through line 53 to a caustic treater 54 in which it is intimately mixed with alkali in a suitable amount introduced throughline 55. mixturev are maintained in intimate contact for a time suiiicient to effect the desired neutralization, the resulting mixture is withdrawn from treater'54 through line 56. The mixture thus rWithdrawn through line 56 comprises alcohols,

alkali salts of organic acids and excess alkali (and may also comprise other non-acid oxygenated organic compounds as originally present in the oil product liquid phase withdrawn from separator I3). In order to facilitate separation of excess alkali and alkali salts of organic acids from this mixture in line 56, the mixture is next transferred to a mixer 51 in which it is contacted with water introduced through line 58. The amount of water is limited to the minimum necessary to eiect separation of the oil soluble components from excess alkali and alkali salts of organic acids, and also to dissolve any relatively low boiling alcohols that may be present, which may include butanol and lighter alcohols. The result- 4ingaqueous mixture from mixer 51 is next transferred through line 59 to a settler 60. In settler 60 the mixture separates into an upper oil phase, which is withdrawn through line 6I, and a lower aqueous phase which is Withdrawn through line 62. This aqueous phase in line 62 comprises an aqueous mixture of excess alkali, alkali salts of organic acids and may also include esters, relatively low boiling alcohols and aldehyde polymers. The mixture thus obtained may next be employed,

in the present modification of the process of the invention, for neutralizing the aforementioned acid containing mixture withdrawn from tower I1 through line 20, and transferred into treater 2l.

For this purpose the aforementioned mixture in line 62 may be transferred directly into treater 2| for further use in the process hereinbefore described. Y

The oil separated in settler 60 and withdrawn as an upper liquid phase through line 6I may next be transferred through this line to a fractionation tower 63. Tower 63 is provided and suitably equipped to separate the oil into several Thus there may be separated a relatively low boiling fraction containing constituents boiling up to 200 F. and containing no alcohols boiling above butanol. This fraction may be withdrawn through line 64. This fraction is relatively free of oxygenated organic compounds and is in condition for further use or treatment outside the scope of The highest boilingl fraction from tower 63 is withdrawn through line 65 as a bottoms condensate. This fraction preferably eontains constituents higher boiling than about 430 F., and comprises relatively high boiling hydrocarbons and aldehydes, and may be withdrawn through line 65 for further use or treatment outside the scope of the present process. An intermediate .boiling fraction from tower After the components of the -minor proportion, which comprises:

163 boiling between about 200 F. and 430 F. may be withdrawn through line 66. This fraction -contains in addition to hydrocarbons, alcohols connects, for further treatment in tower 3| as hereinbefore described, in order to remove any hydrocarbonV impurities that may be present in the alcohol mixture in line 68. While a particular intermediate boiling oil fraction has been indicated as being withdrawn from tower 63 through line 61, it will be understood of course, that any intermediate boiling fraction within the range 4from about 200 F. and 430 F. may also be withdrawn from this tower and subjected to similar treatment in the process indicated above.

Having thus described our invention, we claim:

1. A process for recovering organic acids and alcohols contained in a water product liquid phase obtained from the treatment of the reaction product produced in the catalytic hydrogenation of oxides of carbon, said water product liquid phase containing hydrocarbons in distilling said water product liquid phase to obtain a relatively high boiling fraction comprising organic acids and a relatively low boiling fraction comprising alcohols and hydrocarbons; subjecting said relatively low boiling fraction to solvent extraction with a relatively low boiling hydrocarbon to produce an extract phase comprising hydrocarbons and a raffinate phase comprising alcohols; and separating the phases thus produced.

2. A process for recovering organic acids and alcohols contained in a Water product liquid `phase obtained from the treatment of the reaction product produced in the catalytic hydrogenation of oxides of carbon, said Water prod- `uct liquid phase. containing hydrocarbons in -subjecting the remainder of said mixture to solvent extraction with a relatively low boiling hyldrocarbon to produce an extract phase comprising hydrocarbons and a raiiinate phase comprising alcohols; and separating the phases thus produced.

V3. A process for recovering organic acids and valcohols contained in a water product liquid 65` phase obtained from the treatment of the reaction product` produced in the catalytichydrogenation of oxides of carbon, said water product liquid phase containing hydrocarbons in minor proportion and aldehydes, which comprises: distilling saidwater product liquid phase to obtain a relatively high boiling fraction comprising organic acids and a relatively low boil- ;ing fraction comprising alcohols, organic acids, `aldehydes and hydrocarbons; contacting said :relatively low boiling fraction with. alkali man acaban and a water productliquid phase-each of .said `phasesfcontaining.organic acids and alcohols, -the method. for recovering organic acids and alcohols-ffromrsaid Water productliquid phase, which comprises: distilling.. said Water product. liquid phaseto obtainfa relatively highboiling fraction comprising organic acids and a relatively low boiling. fraction comprising alcohols and organic acids; neutralizing at. least aportion. of said oil productliquid phase. toV obtain a mixture comprising alcohols, alkalisalts of organic acids and excess alkali; separating alkali salts and excess alkalirom themixture thus obtained; neutralizsaid relatively low boiling fraction with said separated alkali saltsand excess alkali to obtain a. mixture comprising alcohols and alkali salts of.. organic acids.; andseparating. alcohols from alkali saltsin the mixture thusproduced.

5. In afprocess for the.catalyticihydrogenation of-.oxidesof carbon to produce .organic compounds in. which, the reaction.. product therefrom is treated. to form anoilproductliquid phase and at vvater product .liquidphasaeach of saidphases containing. organic. acids and alcohols and said Water product.. liquid. phase. containing hydrocarbonsv in .minor proportion, the. methodr for recovering `organic acids and alcohols from said Water product liquid phase, which comprises: distillingsaidwater product liquid phase to. obtain a. relativelyy high boiling yfraction comprising; organic. acids.-v and' a relatively lo'w boiling fractionv comprising alcohols, organic acids and hydrocarbons; neutralizing at least a portion of saidV oilproduct liquid phase to obtain amixture comprising, alcohols/alkali saltsk ofv organic acids and excess alkali; separating'alkali salts and excess alkali. from the mixture thus obtained; neutralizing said relatively loW'boiling fraction with said separated alkali'salts and excess alkali tofobtain a mixture. comprising alcohols', alkali salts of" organic acids and' hydrocarbons; sepa'- rating, alkali salts fromv the mixture thus pro'- duced; subjectingl theV remainder of said mixture to solvent extraction with' al relatively low boiling hydrocarbon to produce'V an extract phase comprising hydrocarbons: andv a ranate phase comprising alcohols; and* separating the phases thus produced.

6. In a process for the catalytic hydrogenation of oxides ofA carbon to produce organic compounds in'which the reaction product therefrom is' treated to form an oil product liquid phase anda Water product liquid phase, each of saidv phases containing organic acids and alcohols'and Said Water product liquid phase containing aldehydes as additional components, the method for' recovering organic acids and alcohols' from said Watereproduct liquidphasewhich comprises: distilling said waterfproduct'liquid phase to obtain a relatively high boiling fraction comprising' organic acids and a relativelylow boiling fraction comprising alcohols,` organic acids .andv aldehydes; neutraliz- 7. In a process for the catalytic hydrogenation of oxides ofA carbonto produce organic compounds in Which the reaction product therefrom is treated to form an oil product liquid phase and a water product'liquid phase, each of said phases containing organic acids and alcohols and said water product liquid phase containing hydrocarbons in minor proportion and aldehydes, the method for recovering organic acids and alcohols from said Water product liquid phase, Which comprises: distilling said Water product liquid phase to obtain a relatively high boiling fraction comprising organic acids and a relatively 10W boiling fraction comprising alcohols, organic acids, aldehydes and hydrocarbons; neutralizing at least a portion of said oil product liquid phase to obtain a, mixture comprising alcohols, alkaliY salts of organic acids and excess alkali; separatingalkali salts and excess alkali from the mixture thusv obtained; contacting said relatively low boiling fraction With said separated alkali salts and excess alkali in an amount sufii'cient to obtain a mixture comprisingalcohols,.alkali salts of organic acids, aldehyde polymers and hydrocarbons; separating alkali salts and aldehyde polymers fromthemix.- ture thus produced; subjecting'the remainderof said mixture to solvent extraction with a relatively low boilingV hydrocarbon to produce an extract phasev comprising hydrocarbons and a rafnate phase comprising alcohols; and separating the phases thus produced. 8. In a process for the catalytic hydrogenation of oxides of carbon to produce organic compounds in which the reaction product therefrom is treated to form an oil product liquid phase and a Water product liquid phase, each of. said phases containing organic acids and alcohols'and said Water product liquid phase containinghydrocarbons.inaminor proportion, the method for recovering organic acids and alcohols fromsaid reaction product which comprises: Water-Washing at least a portion of said oil product liquid phaseto obtain a mixture. of hydrocarbons and Water containing dissolved organic acids` and alcohols; separating said mixture from said oil product liquid phase; combining the mixture thus separated with said Water product liquid phase; distilling the. resulting mixture to obtain a relatively high boiling fraction. comprising 0I'.- ganic acids and a relatively lowboiling fraction comprising alcohols and hydrocarbons; subjecting said, relatively low boiling fraction to solvent extraction with a relatively low boiling hydrocarbon to produce an extract phase comprising hydrocarbons and a railinate phase comprising alcohols; and' separatingk the phases thus produced.

9. VIn a. process for the catalytic hydrogenation of oxides of carbon toproduce organic compounds in" which the reaction product therefrom is treatedtov form an oilproduct liquid phase and a Water product liquid phase, each of said phases containing organic acids and alcoholsl and said Water product liquid phase containing hydrocarbons in minor proportion, the method for recovering organic acids and alcohols from said reaction prod uct which comprises: Water-Washing at least a portion of said oil product liquid phase to obtain a mixture of hydrocarbons and Water containing dissolved organic acids and alcohols; separating said mixture from said oil product liquid phase; comibning the mixture thus separated with said water product liquid phase; distilling the resulting mixture to obtain a relatively high boiling fraction comprising organic acids and a relatively loW boiling fraction comprising alcohols, organic acids and hydrocarbons; neutralizing said relatively low boiling fraction to obtain a mixture comprising alcohols, alkali salts of organic acids and hydrocarbons; separating alkali salts from said mixture; subjecting the remainder of said mixture to solvent extraction with a relatively low boiling hydrocarbon to produce an extract phase comprising hydrocarbons and a rafiinate phase comprising alcohols; and separating the phases thus produced.

10. In a process for the catalytic hydrogenation of oxides of carbon to produce organic compounds -in which the reaction product therefrom is treat- 'ed to form an oil product Vliquid phase and a Water product liquid phase, each of said phases containing organic acids and alcohols and said Water product liquid phase containing hydrocarbons in minor proportion and aldehydes, the method for recovering organic acids and alcohols from said reaction product Which comprises: water-Washing at least a portion of said oil product liquid phase to obtain a mixture of hydrocarbons and Water containing dissolved organic acids and alcohols; separating said mixture from said oil product liquid phase; combining the mixture thus separated with said Water product liquid phase; distilling the resulting mixture to obtain a relatively high boiling fraction comprising organic acids and a relatively low boiling fraction comprising alcohols, organic acids, aldehydes and hydrocarbons; contacting said relatively lovv boiling fraction With alkali in an amount suicient to obtain a mixture comprising alcohols, alkali salts of organic acids, aldehyde polymers and hydrocarbons; separating alkali salts and aldehyde polymers from said mixture; subjecting the remainder of said mixture to solvent extraction with a relatively7 low boiling hydrocarbon to produce an extract phase comprising hydrocarbons and a raffinate phase comprising alcohols; and separating the phases thus produced.

11. In a process for the catalytic hydrogenation of oxides of carbon to produce organic compounds in Which the reaction product therefrom is treated to form an oil product liquid phase and a Water product liquid phase, each of said phases containing organic acids and alcohols,vthe method for recovering organic acids and alcohols from said reaction product which comprises: Water-Washing at least a portion of said oil product liquid phase to obtain a mixture comprising organic acids and alcohols; separating said mix- Vture from said oil product liquid phase; combining the mixture thus separated With said Water product liquid phase; distilling the resulting mixture to obtain a relatively high boiling fraction comprising organic acids and a relatively loW boiling fraction comprising alcohols and organic acids; neutralizing at least a portion of said water-Washed oil product liquid phase to obtain a mixture comprising alcohols, alkali salts of organic acids and excess alkali; separating alkali salts and excess alkali from the mixture boiling fraction with said separated alkali 'salts and excess alkali to obtain a mixture comprising alcohols and alkali salts of organic acids; and separating alcohols from alkali salts in the mixture thus produced. I

` l2. In a process for the catalytic hydrogenation of oxides of carbon to produce organic compounds in which the reaction product therefrom is treated to form an oil product liquid phase and a Water product liquid phase, each of said phases con-'l taining organic acids and alcohols and said Water-product liquid phase containing hydrocarb ons in minor proportion, the method for recovering organic acids and alcohols from said reactionl product which comprises: water-Washing at least aportion of said oil product liquid phase' to obtain a mixture of hydrocarbons and water containing dissolved organic acids and alcohols;`V separating said mixture from said oil product liquid phase; combining the mixture thus sep-Y arated With said water product liquid phase; distilling the resulting mixture to obtain a relatively high boiling fraction comprising organic acids and a relatively low boiling fraction comprising alcohols, organic acids andvhydrocarbons; neutralizing at least a portion of said Water-washed oil product liquid phase to obtain a mixture comprising alcohols, alkali salts of organic acids and excess alkali; separating alkali salts and excess alkali from the mixture thus obtained; neutralizling said relatively low boiling fraction with said separated alkali salts and excess alkali to obtain a mixture comprising alcohols, alkali salts of organic acids and hydrocarbons; separating ,alkali salts from the mixture thus produced; subjecting the remainder of said mixture to solvent extraction with a relatively low boilingvhydrocarbon to produce an extract phase comprising hydrocarbons and a raiiinate phase comprising alcohols; and separating the phases thus produced. y

13, In a process for the catalytic hydrogenation of oxides of carbon to produce organic compounds in which the reaction product therefrom is treated to form an oil product liquid phase and a water product liquid phase, each of said phases containing organic acids and alcohols and said water product liquid phase containing aldehydesas additional components, the method for recovering organic acids and alcohols from said reaction product which comprises: Water-Washing at least a portion of said oil product liquid phase to obtain a mixture comprising organic acids and alcohols; separating said mixture from said oil product liquid phase; combining the mixture thus separated Withsaid water product liquid phase; distilling the resulting mixture to obtain a relatively high boiling fraction comprising organic acids anda relatively loW. boiling fraction comprising alcohols, organic acids and aldehydes; neutralizing at least a portion of said water- Washed oil product liquid phase to obtain a mixvture comprising alcohols, alkali salts of organic acids and excess alkali; separating alkali salts and excess alkali from the mixture thus obtained; contacting said relatively low boiling fraction With said separated alkali salts and excess alkali in an amount suiii'cient to obtain a mixture comprising alcohols, alkali salts of organic acids and aldehyde polymers; and separating alcohols from alkali salts and aldehyde polymers in the mixture thus produced.

14. In a process for the catalytic hydrogenation of oxides of carbon to produce organic com--z Vfa,csls,111

13 pounds in which the reaction product therefrom is treated to form an oil product liquid phase and a Water product liquid phase, each of said phases containing organic acids and alcohols and said Water-product liquid phase containing hydrocarbons in minor proportion and aldehydes,

the method for recovering organic acids and alcohols from said reaction product Which comprises: water-Washing at least a portion of said oil product liquid phase to obtain a mixture comprising organic acids and alcohols; separating said mixture from said oil product liquid phase; combining the mixture thus separated With said Water product liquid phase; distilling the resulting mixture to obtain a relatively high Vboiling fraction comprising organic acids and a relatively low boiling fraction comprising alcohols, organic acids, aldehydes` and hydrocarbons; neutralizing at least a portion of said water-washed oil product liquid phase to obtain a mixture comprising alcohols, alkali salts of organic acids and excess alkali; separating alkali salts and excess alkali from the mixture thus obtained; contacting said relatively W boiling fraction with said separated alkali salts and excess alkali in an amount suicient to obtain a mixture comprising alcohols, alkali salts of organic acids, aldehyde polymers and hydrocarbons; separating alkali salts and aldehyde polymers from the mixture thus produced; subjecting the remainder oi said mixture to solvent extraction with a relatively low boiling hydrocarbon to produce an extract phase comprising hydrocarbons and a raffinate phase comprising alcohols; and separating the phases thus produced.

15. In a process for the catalytic hydrogenation of oxides of carbon to produce organic com- Y pounds in which the reaction product therefrom is treated to form an oil product liquid phase and a Water product liquid phase, each of said phases containing organic acids and alcohols, the method for recovering organic acids and alcohols from said reaction product which comprises: water-washing at least a portion of said oil product liquid phase to obtain a mixture of hydrocarbons and Water containing dissolved organic acids and alcohols; separating said mixture from said oil product liquid phase; combining the mixture thus separated with said Water product liquid phase; distilling the resulting mixture to obtain a relatively high-boiling fraction comprising organic acids and a relatively low-boiling fraction comprising alcohols and hydrocarbons; subjecting said relatively low-boiling fraction to solvent extract with a relatively low-boiling hydrocarbon to produce an extract phase comprising hydrocarbons and a rafnate phase compris- 14 ing alcohols; and separating the phases thus produced.

16. In a process for the catalytic hydrogenation of oxides of carbon to produce organic cornpounds in Which the reaction product therefrom is treated to form an oil product liquid phase and a water product liquid phase, each or said phases containing organic acids and alcohols, the method for recovering organic acids and alcohols from said reaction product which comprises: water-Washing at least a portion of said oil product liquid phase to obtain a mixture comprising organic acids and alcohols; separating said mixture from said oil product liquid phase; combining the mixture thus separated with said Water product liquid phase; and distilling the resulting mixture to obtain a relatively high-boiling fraction comprising organic acids and a relatively low-boiling fraction comprising alcohols.

17. In a process for the catalytic hydrogenation of oxides of carbon to produce organic compounds in which the reaction product therefrom is treated to form an oil product liquid phase and a Water product liquid phase, each of said phases containing organic acids and alcohols and said Water product liquid phase containing aldehydes, the method for recovering organic acids and alcohols from said reaction product which cornprises: Water-'Washing at least a portion of said oil product liquid phase to obtain a mixture comprising organic acids and alcohols; separating said mixture from said oil product liquid phase; combining the mixture thus separated with said Water product liquid phase; distilling the resulting mixture to obtain a relatively high boiling fraction comprising organic acids and a relatively low-boiling fraction comprising alcohols, organic acids and aldehydes; contacting said relatively low-boiling fraction with alkali in an amount suiiicient to obtain a mixture comprising alcohols, alkali salts of organic acids and aldehyde polymers; and separating alkali salts and aldehyde polymers from said mixture.

HENRY G. MCGRATH. HERBERT J. FASSINO. LOUIS C. RUBIN.

References Cited in the le of this patent UNITED STATES PATENTS Number Name Date 2,274,750 Soenksen et al. Mar. 3, 1942 2,288,769 Alleman et al July 7, 1942 2,476,788 White July 19, 1949 2,519,127 Lauer et al July 25, 1950 2,533,675 Marschner Dec. 12, 1950 

1. A PROCESS FOR RECOVERING ORGANIC ACIDS AND ALCOHOLS CONTAINED IN A WATER PRODUCT LIQUID PHASE OBTAINED FROM THE TREATMENT OF THE REACTION PRODUCT PRODUCED IN THE CATALYTIC HYDROGENATION OF OXIDES OF CARBON, SAID WATER PORDUCT LIQUID PHASE CONTAINING HYDROCARBONS IN MINOR PROPORTION, WHICH COMPRISES: DISTILLING SAID WATER PRODUCT LIQUID PHASE TO OBTAIN A RELATIVELY HIGH BOILING FRACTION COMPRISING ORGANIC ACIDS AND A RELATIVELY LOW BOILING FRACTION TO SOLVENT EXPRISING ALCOHOLS AND HYDROCARBONS; SUBJECTING SAID RELATIVELY LOW BOILING FRACTION TO SOLVENT EXTRACTION WITH A RELATIVELY LOW BOILING HYDROCARBON TO PRODUCE AN EXTRACT PHASE COMPRISING HYDROCARBONS AND A RAFFINATE PHASE COMPRISING ALCOHOLS; AND SEPARATING THE PHASES THUS PRODUCED. 